Furfuryl alcohol-resorcinol resin composition



Patented Feb. 22, 1949 FURFURYL ALCOHOL-RESORCINOL RESIN COMPOSITION John Delmonte, Glendale, Calif., assignor, by direct and mesne assignments, of seventy-two per cent to Ralph Hemphill, Los Angeles, Calif.

No Drawing. Application June 30, 1944, Serial No. 543,044

Claims. (Cl. 260-42) 3 This invention relates to resinous products, and in particular to resorcinol-containing resins condensed or polymerized under alkaline conditions with furane derivatives such as furiuraldehyde and furfuryl alcohol.

Furfuryl alcohol, alone or with furfural, in the 5 ties. An alkaline catalyst is used, and the reacpresence of acids as catalysts, is known to form tion is exothermic. The product may be advanresinous bodies by condensation and polymerizatageously used for laminating and impregnating tion. I have found that liquid resinous bodies fabrics and the like. may be produced in the presence of alkaline I may vary the proportions of resorcinol and catalysts by the interaction of resorcinol with furfuryl alcohol over a fairly wide range, for exfurfuryl alcohol as well as with furfural. I have ample from 1:2 to 3:1 mole weights of the inalso discovered that the liquid resinous materials gredients, with some variations in the properties thus formed between furfuryl alcohol and re-, of the liquid resins, the increase in proportion sorcinol, or between furfural and resorcinol, may of the alcohol giving resins of lesser viscosity advantageously be used as an addition material under otherwise similar conditions of polymerizato the furane resin described in my co-pending tion. I prefer approximately equal numbers of application Serial No. 518,403, filed January 15, moles of the two ingredients. The amount of 1944', now abandoned, which consists of mixtures alkaline catalyst may also be'varied, and I may of furfuryl alcohol and furfural polymerized and use sodium or potassium carbonate, or hydroxide, condensed in the presence of acid catalysts. The or other alkaline reagents, it being required that addition of either resorcinol-furfuryl alcohol or the mixture bealkaline to at least pH 8.0. resorcinol-furfural to my acid catalyzed furane The liquid resins so produced are quite stable resin efiects a combination which may be catabut may be converted over to solid, infusible, inlyzed and resinified under alkaline conditions. soluble resins by the addition of an acid in suffi- Heretofore, the resinification of furfural-furfuryl cient quantity t chang the condition to acidic. alcohol resins has been possible only under acid The exact nature of the polymerization'reaction conditions, and there ar advantages resulting under alkaline conditions is not fully understood, from the use of an alkaline at ys ns d of a but it has been observed that water is not given acid one. The alkali catalyzed resinification of oil as a product of the reaction, perhaps indicating resorcino w th furflllyl 31001101 pp to be that it is not an ordinary condensing reaction Specific to resorcinol as I have found that resins or polymerization, involving a' carbon to carbon are not formed when phenol, or naphthol are sublinkage thr u h the furane rin stituted for th re o in y mixtures. In forming my'resins with resorcinol I'have Illustr tiv of my new furfuryl-alcohol-resorcifound that a pure C. P. grade of resorcinol is not 10 liquid resins, I e brought together equal necessary, and small percentages of other ingredimolar weights of furfuryl alcohol and of resorcim such as catechol and phenolics may be 2101, with from one to three parts per hundred of r t; sodium carbonate, and heated the mixed liquids, 40 I have found the reaction of resorcinol with with a reflux condenser arrangement to avoid loss furfural to be much more vigorous than with furof volatile materials, until a thick liquid resin is furyl alcohol. It is advantageous to employ mildly obtained. The viscosity of a given mixture of inalkaline conditions. When heating the preferred gredients depends upon the time of heating. For equi-molecular proportions of furfural and reexample, using the indicated equal mole weight sorcinol, the reaction may advantageously be carproportions and heating at 250 to 300 F. for one ried out in an open vessel because it is quite to two hours, a liquid of more than 300 centivigorous even below the boiling points of the conpoises is produced. Further additions of alkaline stituents,and cooling may be required to control catalyst will efiect further resinification, although the reaction. Small additions of acetic acid may even prolonged heating gives only a thermoplasbe used to inhibit the reaction. A thick liquid 2 tie liquid polymer. To this liquid polymer may be added, preferably in equal molar proportions, furfural, and further resinification results. The addition of furfural to the liquid resorcinol-furfuryl alcohol resin imparts thermosetting quali- 'cosity of about 100 centipoises.

resin is obtained with a viscosity above 1000 centipoises. This liquid resin added to furfural-furfuryl alcohol acid-catalyzed resins will effect a combination which maybe catalyzed by alkali catalysts. The products of this reaction are distinguished by good adhesive properties for aluminum and its ability to develop high strength at low temperatures, under 130 F. Low pressure curing resins for casting, and low pressure liquid resins for laminating have been prepared from these materials.

I have also made liquid resorcinol-furfural resins in the proportions of one mole of resorcinol to two moles of furfural, although these are not as satisfactory as the mixture with equi-molecular proportions. The liquid resorcinol-furfural resin thickens and solidifies at room temperature in a few days unless blended with the liquid furfural-furfuryl alcohol resins inhibited by means of volatile amines and the like. On the other hand I may arrest resiniflcation of the resorcinol-furfural resin by dissolving it in an alcohol or acetone solvent. As such it exhibits excellent properties as a laminating varnish for impregnating cloth or paper for hot pressing.

I may substitute acid catalyzed furfuryl alcohol-formaldehyde resins for the acid catalyzed furfural-furfuryl alcohol resins in the combinations with the liquid furane-resorcinol resins above described, to produce mixtures which may be further catalyzed to solid resins in the presence of alkali catalysts.

One important use for the liquid resorcinolfurfuryl alcohol or liquid resorcinol-furfural resins is an addition agent to the series of resins known in the trade as Resin X, which consists of acid catalyzed furfuryl-alcohol-furfural mixtures. This addition permits the "Resin X" to be catalyzed under alkaline conditions which has heretofore not been possible. The necessity of using an acid catalyst has, in some cases particularly where oellulosic materials are present, limited the applications of Resin X, whereas by using the new liquid resins catalyzed by alkaline catalysts, and mixing these with partly polymerized acid catalyzed furfural-furfuryl alcohol mixtures (Resin X") it is possible to overcome these objections.

In my preferred practice, I resinifyunder acid catalyst conditions a suitable mixture of furfuryl alcohol and ,furfurai to a product having a vis- In general, I prefer to carry this reaction to as high viscosity liquid as can readily be mixed with the other con stituent. If this resin is not used immediately, the further polymerization may be temporarily inhibited by adding a volatile basic reagent such as a tertiary amine (for examples, triethylamine, trimethylamine, triethanolamine, etc.) in an amount to give a pH above 3.5. To this resinous liquid is added a viscous (preferably 50 to 500 centipoises) furfuryl alcohol-resorcinol, or furfural-resorcinol resin, made as described above.

.The "Resin X" of viscosities from 10 to 2000 centipoises has been employed but the fluid product which I prefer may best be made by using the viscosities indicated. An alkali catalyst is then added, for example, 2 to 10 parts by weight of approximately twenty percent water solution of caustic soda to each 100 parts of the mixed resins. Some exothermic heat is generated, and the resin combination'sets at ordinary room temperatures without the application of external heat. I may,

' however. use less alkaline catalyst and complete the resiniflcation with heat.

For the alkaline catalyst I may use, besides the caustic alkali solution, any suitable inorganic or organic compound which yields a strong alkaline solution in the presence of water, and which does not otherwise adversely affect the reaction here involved, including for examples the caustic alkalies, alkali metal carbonates, ammonium hydroxide, ammonium hydrosulflde, alkyl substituted ammonium hydroxides, and alkamines. Where the terms "alkalif or alkaline" catalyst is used in .these specifications and claims. it is meant to include the specific reagents mentioned and any others equivalent thereto in the reactions herein described.

Myalkali catalyzed resin may be used in liquid form before setting to a solid, as an adhesive, or it may be molded or cast into shapes, or used for paper or fabric lamination products.

Wide variations in the proportions of ingredients may be used, and eight compositions are here given for illustration. In the first six examples, the alkali catalyzed resin 0! resorcinol with either furfuryl alcohol, or furfural, are in equimolecular proportions, while the Resin 1 (furfural-furfuryl alcohol acid catalyzed) component, has its composition varied as indicated.

Example I Example II Parts by weight Furfuryl alcohol-resorcinol, alkali catalyzed resinv 1 60% furfuryl alcohol-30% furfural, acid catalyzed resin 2.25

A 20% caustic soda solution in water .35

Example In I Parts by weight Furfural-resorcinol, alkali catalyzed resin..- 10

70% *furfuryl alcohol30% furfural, acid catalyzed resin: 10

A 20% caustic soda solution in water 1 Example IV Furfuryl alcohol-resorcinol, alkali catalyzed resin furfuryl alcohol-10% i'urfural. acid catalyzed resin 10 A 20% caustic soda solutionin water 1.3

Example V Parts by weight Furfural-resorcinol, alkali catalyzed resin... 10 50% furfuryl alcohol-40% furiural, acid catalyzed resin A 20% caustic soda solution in water 1 Example VI 7 I l Parts well ht Furfuryl alcohol-resorcinol, alkali catalyzed resin Furfural-furfuryl alcohol, equal parts. acid catalyzed resin A 20% caustic soda solution. Jo

Parts by Example VII Parts by weight Fuiuryl alcohol-resorcinol resin Furfural 7.5 Triethanolamine 2 The furfuraldehide in this composition may be varied from 5 to 10 parts by weight, and the triethanolamine from 1 to 3 parts with similar results.

Etvample VIII Parts by weight Furfuryl alcohol-resorcinol resin 10 Furfural containing 50 percent polyvinyl acetate in solution 10 Triethanolamine 2 All of these combinations are eflectively polymerized under alkaline conditions, to give homogeneous, strong, solid resins. When the two components, the acid catalyzed resin and the alkali catalyzed resin are mixed together with the additional alkali catalyst, the mixture becomes warm by exothermic heat, and the resin sets up to a hard strong body without externally applied heat. The best or optimum range of properties of the finished resins appears to be the compositions having a molecular proportion of furfural in excess of resorcinol, a slight excess for the iurfuryl alcohol-resorcinol liquid resin addition agent, and a large excess for the resorcinol-iurfural resin, addition agent.

In the table are shown some typical shear strengths. These were measured by pulling apart aluminum strips which had been cemented together under uniform conditions of curing for 48 hours at 120 F. after catalyzing the mixture of components with an alkali catalyst.

Parts by weight of acid catalyzed Parts by weight of alkaline cat- Shear Resin, 2moles i'uralyzed Resin oi the mo! ccmstrength, iuryl alcohol to 1 position shown p. s. i. moi iurlural l (1% RBSOL-l iurluryl alc.) 350 1 (1% Resor.-1 i'uriuryl alc.) 100 l (1% RGSOL-l lurfuryl alc.). 175 l (i Remix-1% furiuryl ale.) 200 l (l Resoia-L iuriuryl ale). 75 l (1 Reson-l luriuryl alc.). 50 l (l Resor.-1 iuriuryl ale.) 500 l (l Resor.-l iurfuryl alc.) 100 l (i Resor.-l iuriuryl alc.). 50 l (l Resor.-l iuriuraDfi. 900 l (l Boson-1 iuriuralL. 500 1 (l Resor.-l iurfural) 800 The compression strengths of typical cured cast samples also show similar trends as shown for shear strengths. For example, 1 part of resorcinol-furfural resin to 1.35 parts of furfuralfurfuryl alcohol resin will cure at 120 F. to a compressive strength of 9000 p. s. i., while 2 parts of the Resin X to 1 part of resorcinol-iurfural will cure to a strength of only 2000 p. s. i. under similar conditions. Under the same low temperature cure conditions, 2 parts of Resin X to 1 part of iuriuryl alcohol-resorcinol will have a strength of 2500 p. s. i., while 1:1 and 3:1 rations of these resins will have less than 1000 p. s. i. compressive strength. All of these resins are alkali catalyzed. The'addition of liquid furfural to resorcinol-furfuryl-alcohol resinsyields a series of liquid low temperature curing resins which show a peak in physical characteristics around equimolar proportions, for example, a compression strength of 7000 p. s. i. However, as much as 3 moles furfural to 1 mole of the resorcinol-furiuryl alcohol resin have been combined with good results.

The Resin X materials modified by the addition of the furfuryl-alcohol-resorcinol resins, and alkaline catalysts, may be used as cold casting resins, or as adhesives, etc. They may be mixed with fillers and coloring materials following the usual practice of the art. Since they become solid without the application of externally applied heat, the methods used for forming into shapes, or into laminated structures, may be greatly simplified, expedited, and lowered in cost. An important application of the resorcinol-furfuryl alcohol resin with added ,furfural, with or without dissolved thermoplastics such as polyvinyl acetate, is for low pressure laminating.

' Cloths of canvas or glass fiber may be impregnated and cured at low temperatures under 200 F. in the presence of air. This is a marked advantage over the present practice of laminating which requires absence of air for other allyl-type thermosetting resins. My resin may be advan tageously employed in bonding wood, because of the use of alkaline catalysts.

While I have described and illustrated my invention by specific examples, I do not wish to be limited to the specific compositions shown, but restrict my invention only insofar as required by the prior art and the spirit of the appended claims.

I claim:

1. A liquid polymer resin comprising the product resulting from heating a mixture of resorcinol and furfurylalcohol in proportions ranging from 1 mole resorcinol for each two moles of furfuryl alcohol, to three moles resorcinol for each one male of furfuryl alcohol, in the presence of an alkali catalyst in an amount to give a pH of at least 3.0.

2. A liquid polymer resin comprising the product resulting from heating a mixture of resorcinol and furfuryl alcohol in equal mole proportions, in the presence of an alkali catalyst in an amount to give a pH of at least 8.0.

3. A resinous material consisting of the product resulting from reacting in the presence of an alkali catalyst a mixture consisting of (a) the product resulting from condensing and polymerizing a mixture of furfuryl alcohol-and furfural, and (b) a liquid resin comprising the product resulting from heating a mixture of resorcinol and furfuryl alcohol in the presence of an alkali catalyst in an amount to give a pH of at least 8.0 the proportion of the resorcinol to furfuryl alcohol being in the rang from 1:2 to 3:1 mol weights of said ingredients.

4. A resinous material consisting of the product resulting from reacting in the presence of an alkali catalyst a mixture consisting of (a) the liquid product resulting from condensing and polymerizing a mixture of two moles of i'urfuryl alcohol and one mole of furfural, and of (b) a liquid resin comprising the product resulting from heating furfuryl alcohol and resorcinol in equal molecular proportions in the presence 0! an alkaii catalyst in an amount to give a pH of at least 8.0.

5. A thermosetting resin comprising the product resulting from reacting in the presence of an alkali catalyst a mixture consisting of (a) furfural in which is dissolved a furfural-soluble thermoplastic polymer resin, and (b) a resin resulting from heating a mixture of furfuryl alcohol and resorcinol in the presence of an alkali catalyst in an amount to give a pH of at least 8.0 the proportions of furfuryl alcohol to resorcinol being in the range from 2:1 to 1:3 mol weights or the ingredients.

JOHN DELMONTE 1 8 amauoas mm The following references are of record in the file of this patent:

UNITED STATES PATENTS Reineck Jan. 16, 1945 

